Diarylboron ester and thioester fungicidal agents

ABSTRACT

There are provided fungicidal diarylboron esters and thioesters having the structural formula ##STR1## Further provided are compositions and methods for the protection of plants from fungal infestation and disease.

BACKGROUND OF THE INVENTION

Phytopathogenic fungi are the causal agents for many diseases that infect and destroy crops. In particular, the diseases apple scab, tomato early blight and grape and pepper botrytis are especially devastating.

In spite of the commercial fungicides available today, diseases caused by fungi still abound. Accordingly, there is ongoing research to create new and more effective fungicides for controlling or preventing diseases caused by phytopathogenic fungi.

SUMMARY OF THE INVENTION

The present invention describes fungicidal diarylboron ester and thioester compounds.

The fungicidal diarylboron ester and thio-ester compounds useful in the methods and compositions of the present invention have the structural formula: ##STR2## wherein X and Y are each independently hydrogen, halogen, C₁ -C₆ alkoxy, C₁ -C₆ haloalkoxy, C₁ -C₆ alkyl or C₁ -C₆ haloalkyl;

m and n are each independently an integer of 0, 1, 2 or 3;

A is O or S;

R, R₁, R₂ and R₃ are each independently hydrogen, halogen, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ hydroxy alkyl, cyano, nitro, CH₂ CN, hydroxy, NR₆ R₇, SO₃ R₈ or COR₉, and when taken together, R and R₁, R₁ and R₂ or R₂ and R₃ may form a ring in which RR₁, R₁ R₂ or R₂ R₃ is represented by the structure: --CH═CH--CH═CH-- or --(CH₂)₄ --;

R₄ is hydrogen, halogen, C₁ -C₈ alkoxy or C₁ -C₈ alkyl;

R₅ is hydrogen, halogen, C₁ -C₈ alkoxy, C₁ -C₈ alkyl, NR₆ R₇, SO₃ R₈, hydroxy, oxo or phenyl optionally substituted with one or more halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups, provided that when R₅ is oxo, R₄ is not present;

W is (CH₂)_(p) ;

p is an integer of 0 or 1;

R₆, R₇ and R₈ are each independently hydrogen or C₁ -C₄ alkyl; and

R₉ is C₁ -C₄ alkyl.

This invention relates to compositions and methods for the prevention, control or amelioration diseases caused by phytopathogenic fungi.

DETAILED DESCRIPTION OF THE INVENTION

Phytopathogenic fungi are the causal agents for many diseases that infect and destroy agronomic crops, both growing and harvested. In the United States alone, agronomic crops must compete with about 18,000 species of fungi. Especially devasting are diseases such as apple scab, tomato early blight, grape or pepper botrytis and the like. Accordingly, there is ongoing research to create new and more effective fungicides for preventing or controlling the vast array of fungal infestations of crops.

Advantageously, the present invention provides a method for the prevention, control or amelioration of a disease caused by a phytopathogenic fungus by contacting said fungus with a fungicidally effective amount of a formula I, diarylboron ester or thioester compound.

The present invention also provides a method for the protection of a plant, plant seed or tuber from fungal infestation and disease by applying to the plant, plant seed or tuber, or to the medium or water in which it is growing, a fungicidally effective amount of a formula I, diarylboron ester or thioester compound.

The fungicidal diarylboron ester and thio-ester compounds of the present invention have the following structural formula I: ##STR3## wherein X and Y are each independently hydrogen, halogen, C₁ -C₆ alkoxy, C₁ -C₆ haloalkoxy, C₁ -C₆ alkyl or C₁ -C₆ haloalkyl;

m and n are each independently an integer of 0, 1, 2 or 3;

A is O or S;

R, R₁, R₂ and R₃ are each independently hydrogen, halogen, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ hydroxy-alkyl, cyano, nitro, CH₂ CN, hydroxy, NR₆ R₇, SO₃ R₈ or COR₉, and when taken together, R and R₁, R₁ and R₂ or R₂ and R₃ may form a ring in which RR₁, R₁ R₂ or R₂ R₃ is represented by the structure: --CH═CH--CH═CH-- or --(CH₂)₄ --;

R₄ is hydrogen, halogen, C₁ -C₈ alkoxy or C₁ -C₈ alkyl;

R₅ is hydrogen, halogen, C₁ -C₈ alkoxy, C₁ -C₈ alkyl, NR₆ R₇, SO₃ R₈, hydroxy, oxo or phenyl optionally substituted with one or more halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups, provided that when R₅ is oxo, R₄ is not present;

W is (CH₂)_(p) ;

p is an integer of 0 or 1;

R₆, R₇ and R₈ are each independently hydrogen or C₁ -C₄ alkyl; and

R₉ is C₁ -C₄ alkyl.

Preferred fungicidal agents of the present invention are diarylboron ester compounds of formula I wherein

X and Y are each independently hydrogen, halogen, C₁ -C₆ alkoxy, C₁ -C₆ haloalkoxy, C₁ -C₆ alkyl or C₁ -C₆ haloalkyl;

m and n are each independently an integer of 0, 1, 2 or 3;

A is O;

R, R₁, R₂ and R₃ are each independently hydrogen, halogen, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ hydroxy-alkyl, nitro, CH₂ CN, hydroxy, NR₆ R₇ or SO₃ R₈, and when taken together, R and R₁, R₁ and R₂ or R₂ and R₃ may form a ring in which RR₁, R₁ R₂ or R₂ R₃ is represented by the structure: --CH═CH--CH═CH--;

R₄ is hydrogen;

R₅ is hydrogen, halogen, C₁ -C₈ alkoxy, C₁ -C₈ alkyl, NR₆ R₇, SO₃ R₈, hydroxy, oxo or phenyl optionally substituted with one or more halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy C₁ -C₄ haloalkoxy groups, provided that when R₅ is oxo, R₄ is not present;

W is (CH₂)_(p) ;

p is an integer of 0 or 1; and

R₆, R₇ and R₈ are each independently hydrogen or C₁ -C₄ alkyl.

More preferred formula I fungicidal agents of the present invention are those wherein

X and Y are each independently hydrogen, halogen or C₁ -C₆ alkyl;

m and n are each independently an integer of 0, 1 or 2;

A is O;

R, R₁, R₂ and R₃ are each independently hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, nitro, NR₆ R₇ or SO₃ R₈, and when taken together, R and R₁ or R₁ and R₂ may form a ring in which RR₁ or R₁ R₂ is represented by the structure: --CH═CH--CH═CH--;

R₄ is hydrogen;

R₅ is hydrogen, SO₃ R₈, oxo or phenyl, provided that when R₅ is oxo, R₄ is not present;

W is (CH₂)_(p) ;

p is an integer of 0 or 1; and

R₆, R₇ and R₈ are each independently hydrogen or C₁ -C₄ alkyl.

Other preferred compounds of the invention include those wherein

X and Y are each independently hydrogen, halogen, or C₁ -C₆ alkyl;

m and n are each independently an integer of 0, 1, 2 or 3;

A is O or S;

R, R₁, R₂ and R₃ are each independently hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, nitro, NR₆ R₇ or SO₃ R₈, and when taken together, R and R₁ or R₁ and R₂ may form a ring in which RR₁ or R₁ R₂ is represented by the structure: --CH═CH--CH═CH--;

R₄ is hydrogen, halogen, C₁ -C₈ alkoxy or C₁ -C₈ alkyl;

R₅ is hydrogen, halogen, C₁ -C₈ alkoxy, C₁ -C₈ alkyl, NR₆ R₇, SO₃ R₈, hydroxy, oxo or phenyl optionally substituted with one or more halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups, provided that when R₅ is oxo, R₄ is not present;

W is (CH₂)_(p) ;

p is an integer of 0 or 1; and

R₆, R₇ and R₈ are each independently hydrogen or C₁ -C₄ alkyl.

Especially preferred fungicidal compounds are those wherein

X and Y are each independently hydrogen or halogen;

m and n are each independently an integer of 0, 1 or 2;

A is O;

R, R₁, R₂ and R₃ are each independently hydrogen, C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, and when taken together R and R₁ may form a ring in which RR₁ is represented by the structure: --CH═CH--CH═CH--;

R₄ is hydrogen; and

R₅ is hydrogen.

Formula I diarylboron ester compounds which are particularly effective as fungicidal agents include

1,1-diphenyl-2-oxa-7a-azonia-1-borataindan; 2,3-dihydro-1,1-diphenyl-2-oxa-9b-azonia-1-borata-1H-benz[e]indene;

1,1-bis(p-chlorophenyl)-6-methyl-2-oxa-7a-azonia-1-borataindan; and

1,1-bis(p-chlorophenyl)-2-oxa-7a-azonia-1-borataindan, among others.

The term halogen used herein includes fluorine, chlorine, bromine and iodine. The term "medium" used herein is defined as any environment, including but not limited to artificial nutrients or soil, in which a plant can be kept, live or thrive.

The fungicidal diarylboron ester and thioester compounds of the present invention are particularly useful in the prevention, control or amelioration of diseases such as apple scab, tomato early blight and grape or pepper botrytis. Such diseases are caused by the phytopathogenic fungi Venturia inaequalis, Alternaria solani and Botrytis cinerea, respectively.

Fungicidal diarylboron ester and thioester compounds of formula I may be prepared by reacting a substituted pyridine of formula II with a diarylborinic acid of formula III as shown in Flow Diagram I. ##STR4##

The formula I compounds are also useful for the protection of growing or harvested plants from the damage caused by photopathogenic fungal disease when applied to said plants at a fungicidally effective rate. The effective rate will vary depending upon factors such as the virulence of the target fungus, the environment of the treatment and other ambient conditions. In practice, generally about 20 ppm to about 1,000 ppm, preferably about 50 ppm to about 500 ppm of a formula I compound may be dispersed in a liquid or solid carrier and applied to the plant, seed or tuber, or to the medium or water in which the plant, seed or tuber is growing.

The fungicidal compounds of the invention may be formulated as concentrated solutions, emulsifiable concentrates, flowable concentrates, microemulsions and the like. Said compounds may also be formulated as dry compacted granules, granular compositions, dusts, dust concentrates, suspension concentrates, wettable powders, and the like. Those formulations which lend themselves to seed, tuber, medium, water and/or foliage applications to provide the requisite plant protection are suitable. Such formulations include the formula I compounds admixed with an inert solid or liquid carrier.

It is contemplated that the fungicidal compounds of the invention may be used in conjunction with, or in combination with, a pesticidally effective amount of one or more other pesticides, including but not limited to, anilazine, benalaxyl, benomyl, bitertanol, bordeaux mixture, carbendazim, carboxin, captafol, captan, chlorothalonil, cyproconazole, dichloran, diethofencarb, diniconazole, dithianon, dodine, edifenphos, fenarimol, fenbuconazole, fenfuram, fenpropidin, fenpropimorph, fentin hydroxide, ferbam, flusilazole, flusulfamide, flutriafol, folpet, fosetyl, fuberidazole, guazatine, hexaconazole, imazalil, iprobenfos, iprodione, mancozeb, maneb, metalaxyl, metiram, myclobutanil, nuarimol, ofurace, oxadixyl, oxycarboxin, penconazole, probenazole, prochloraz, propiconazole, pyrazophos, tebuconazole, thiabendazole, thiophanate, thiophanate-methyl, triadimefon, triadimenol, triarimol, tricyclazole, tridemorph, triflumizole, triforine, vinclozolin, and/or zineb.

Where compositions of the invention are to be employed in combination treatments with other pesticidal agents, the composition may be applied concurrently as an admixture of the components as described above, or may be applied sequentially.

In order to facilitate a further understanding of the invention, the following examples are presented primarily for the purpose of illustrating more specific details thereof. The invention should not be deemed limited thereby except as defined in the claims.

EXAMPLE 1 Preparation of 1,1-Diphenyl-2-oxa-7a-azonia-1-borataindan ##STR5##

A mixture of diphenylborinic acid (1.0 g, 5.5 mmol) and 2-pyridinemethanol (0.53 mL, 5.5 mmol) in diethyl ether is refluxed overnight and filtered to obtain the title product as a white solid (1.4 g, mp 150°-152° C.).

Using essentially the same procedure, and employing the appropriately substituted diphenylborinic acid and 2-pyridinemethanol, 1-isoquinolinemethanol or 2-quinolinemethanol, the following compounds are obtained:

    __________________________________________________________________________      ##STR6##                                                                      X Y R      R.sub.1                                                                              R.sub.2                                                                              R.sub.3                                                                               R.sub.5                                                                            mp °C.                                __________________________________________________________________________     H H H      H     H     H      SO.sub.3 H                                                                         291-294                                      F F H      H     H     H      H   239-244                                      H H H      H     CHCHCHCH     C.sub.6 H.sub.5                                                                    225-226                                      H H CHCHCHCH     H     H      C.sub.6 H.sub.5                                                                    180-181                                      H H CHCHCHCH     H     H      H   175.5-176                                    Cl                                                                               Cl                                                                               CH.sub.2 OH                                                                           H     H     H      H   88-90                                        Cl                                                                               Cl                                                                               H      CH.sub.3                                                                             H     H      H   135-143                                      Cl                                                                               Cl                                                                               H      H     H     H      H   133-134                                      __________________________________________________________________________

EXAMPLE 2 Preparation of 2,3-Dihydro-1,1-diphenyl-2-oxa-9b-azonia-1-borata-1H-benz[e]indene-3-one ##STR7##

Diphenylborinic acid (0.77 g, 4.2 mmol) is added to a suspension of quinaldic acid (0.73 g, 4.2 mmol) in an ethanol/water (1:1) solution. The reaction mixture is stirred at room temperature for several days and filtered to give a solid. The solid is dried in a vacuum oven to obtain the title product as a white solid, mp 248°-249° C.

Using essentially the same procedure, but substituting 3-isoquinaldic acid for quinaldic acid, 1,1-diphenyl-2-oxa-9a-azonia-1-borata-1H-benz[f]inden-3(2H)-one is obtained an an off-white solid, mp 244.5°-245° C.

EXAMPLE 3 Preparation of 1,1-Bis(p-chlorophenyl)-1,2,3,4-tetrahydro-2-oxa-8a-azonia-1-boratanaphthalene ##STR8##

A mixture of [(bis-p-chloro)diphenyl]borinic acid (0.45 g, 1.5 mmol) and 2-hydroxyethylpyridine (0.18 g, 1.5 mmol) in diethyl ether is stirred at room temperature for 24 hours and filtered to obtain the title product as a white solid (0.22 g, mp 117°-119° C.).

EXAMPLE 4 Evaluation of in vivo fungicidal activity of test compounds

Test compounds are dissolved or suspended in acetone and diluted with deionized water containing about 0.05% TWEEN 20, a polyoxyethylene sorbitan monolaurate surfactant manufactured by Atlas Chemical Industries, to give a concentration of 200 ppm.

Host plants are sprayed with the test solution, dried and inoculated with fungi. When disease symptom development is optimal, the plants are rated for disease control according to the rating scale shown below. Each test contains inoculated treated plants, inoculated untreated plants and a reference standard. When more than one test is run, the data are averaged. The data obtained are shown in Table I.

Compounds employed in this in vivo fungicidal evaluation and in the in vitro fungicidal evaluation in the following example are given a compound number and identified by name. Data in Table I are reported by compound number.

    ______________________________________                                         RATING SCALE                                                                   Rating      Range % Control                                                    ______________________________________                                         0            0                                                                 1           1-14                                                               2           15-29                                                              3           30-44                                                              4           45-59                                                              5           60-74                                                              6           75-89                                                              7           90-95                                                              8           96-99                                                              9           100                                                                --          no evaluation                                                      ______________________________________                                    

    ______________________________________                                         PHYTOPATHOGENIC FUNGI                                                          Symbol  Disease           Pathogen                                             ______________________________________                                         AS      Apple Scab        Venturia inaequalis                                  GDM     Grape Downy Mildew                                                                               Plasmopara viticola                                  PB      Pepper Botrytis   Botrytis cinerea                                     RB      Rice Blast        Pyricularia oryzae                                   SBC     Sugar Beet Cercospora                                                                            Cercospora beticola                                  TEB     Tomato Early Blight                                                                              Alternaria solani                                    WPM     Wheat Powdery Mildew                                                                             Erysiphe graminis                                                              f. sp. tritici                                       WSN     Wheat Septoria Nodorum                                                                           Septoria nodorum                                             Blotch                                                                 ______________________________________                                    

    ______________________________________                                         COMPOUNDS EVALUATED AS FUNGICIDAL AGENTS                                       Compound No.                                                                   ______________________________________                                         1          1,1-Diphenyl-2-oxa-7a-azonia-1-bora-                                           taindan                                                             2          1,1-Diphenyl-2-oxa-7a-azonia-1-boratain-                                       dan-3-sulfonic acid                                                 3          1,1-Bis(p-fluorophenyl)-2-oxa-7a-azonia-                                       1-borataindan                                                       4          2,3-Dihydro-1,1-diphenyl-2-oxa-9b-azonia-                                      1-borata-1H-benz[e]indene                                           5          1,1-Diphenyl-2-oxa-9a-azonia-1-borata-1H-                                      benz[f]inden-3(2H)-one                                              6          2,3-Dihydro-1,1,3-triphenyl-2-oxa-9a-                                          azonia-1-borata-1H-benz[f]indene                                    7          2,3-Dihydro-1,1,3-triphenyl-2-oxa-9b-                                          azonia-1-borata-1H-benz[e]indene                                    8          1,1-Bis(p-chlorophenyl)-1,2,3,4-tetra-                                         hydro-2-oxa-8a-azonia-1-boratanaphthalene                           9          1,1-Bis(p-chloro-phenyl)-2-oxa-7a-azonia-                                      1-borataindan                                                       10         1,1-Bis(p-chlorophenyl)-6-methyl-2-oxa-                                        7a-azonia-1-borataindan                                             11         2,3-Dihydro-1,1-diphenyl-2-oxa-9b-azonia-                                      1-borata-lH-benz[e]indene-3-one                                     12         1,1-(p-Chlorophenyl)-7-(hydroxymethyl)-2-                                      oxa-7a-azonia-1-borataindan                                         ______________________________________                                    

                                      TABLE I                                      __________________________________________________________________________     In Vivo Fungicidal Evaluations                                                 Compound                                                                              Rate                                                                    Number (ppm)                                                                              AS  GDM PB RB SBC                                                                               TEB WPM WSN                                        __________________________________________________________________________     1      200 9   8   9  0  5  6   0   --                                         2      200 0   0   0  0  0  0   2   0                                          3      200 6   4   0  0  8  8   6   0                                          4      200 6   2   9  6  0  6   0   0                                          5      200 0   0   6  0  0  0   0   0                                          6      200 4   0   0  0  0  0   0   0                                          7      200 0   0   0  0  0  0   0   0                                          8      200 6   7   0  0  0  0   6   0                                          9      200 6   6   5  0  5  3   0   0                                          10     200 8   7   7  0  0  0   0   0                                          11     200 0   0   0  0  0  0   0   0                                          12     200 4   4   7  4  0  2   0   4                                          __________________________________________________________________________

EXAMPLE 5 Evaluation of in vitro fungicidal activity of test compounds

Test compounds are dissolved or suspended in acetone and dispersed into cell well plates containing a suspension of ground fungal mycelia in a nutrient broth. Assay plates are incubated for 3-4 days at 21° C. Growth inhibition is measured visually and is rated using the following scale:

    ______________________________________                                                Rating                                                                               % Inhibition                                                      ______________________________________                                                0      0                                                                       1      1-29                                                                    3     30-59                                                                    5     60-89                                                                    7     90-99                                                                    9     100                                                               ______________________________________                                    

Untreated controls, solvent blanks and reference standards are included in each test.

Assay fungi include the plant pathogens, Pythium ultimum (Pythul); Rhizoctonia solani (Rhizso); Fusarium oxysporum f. sp. cucumerinum (Fusoxc); and Pseudocercosporella herpotrichoides (Psdche).

When more than one test is run, the data are averaged. The data obtained are shown in Table II. The compounds evaluated are reported by compound number given in Example 4.

                  TABLE II                                                         ______________________________________                                         In Vitro Fungicidal Evaluations                                                Com-                                                                           pound                                                                          Num-  Rate                                                                     ber   (ppm)   FUSOXC    PSDCHE  PYTHUL  RHIZSO                                 ______________________________________                                         1     25      9         5       9       9                                      2     25      7         5       7       9                                      3     25      7         5       7       9                                      4     25      9         9       9       9                                      5     25      3         5       5       0                                      6     25      0         0       0       0                                      7     25      3         0       3       0                                      8     25      9         9       9       9                                      9     25      7         9       9       7                                      10    25      5         9       9       7                                      11    25      5         0       7       5                                      12    25      7         9       9       5                                      ______________________________________                                     

I claim:
 1. A method for the prevention, control or amelioration of a disease caused by a phytopathogenic fungus which comprises contacting said fungus with a fungicidally effective amount of a compound having the structural formula ##STR9## wherein X and Y are each independently hydrogen, halogen, or C₁ -C₆ alkyl;m and n are each independently an integer of 0, 1, 2 or 3; A is O or S; R, R₁, R₂ and R₃ are each independently hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, nitro, NR₆ R₇ or SO₃ R₈, and when taken together, R and R₁ or R₁ and R₂ may form a ring in which RR₁ or R₁ R₂ is represented by the structure: --CH═CH--CH═CH--; R₄ is hydrogen, halogen, C₁ -C₈ alkoxy or C₁ -C₈ alkyl; R₅ is hydrogen, halogen, C₁ -C₈ alkoxy, C₁ -C₈ alkyl, NR₆ R₇, SO₃ R₈, hydroxy, oxo or phenyl optionally substituted with one or more halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups, provided that when R₅ is oxo, R₄ is not present; W is (CH₂)_(p) ; p is an integer of 0 or 1; and R₆, R₇ and R₈ are each independently hydrogen or C₁ -C₄ alkyl.
 2. The method according to claim 1 whereinX and Y are each independently hydrogen or halogen; m and n are each independently an integer of 0, 1 or 2; A is O; R, R₁, R₂ and R₃ are each independently hydrogen, C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, and when taken together R and R₁ may form a ring in which RR₁ is represented by the structure: --CH═CH═CH═CH--; R₄ is hydrogen; and R₅ is hydrogen.
 3. The method according to claim 2 wherein the compound is selected from the group consisting of1,1-diphenyl-2-oxa-7a-azonia-1-borataindan; 2,3-dihydro-1,1-diphenyl-2-oxa-9b-azonia-1-borata-1H-benzindene; 1,1-bis(p-chlorophenyl)-6-methyl-2-oxa-7a-azonia-1-borataindan; and 1,1-bis(p-chlorophenyl)-2-oxa-7a-azonia-1-borataindan.
 4. The method according to claim 1 wherein the compound is applied at a concentration of about 20 ppm to 1,000 ppm.
 5. A method for the protection of a plant, plant seed or tuber from fungal infestation and disease which comprises applying to the plant, plant seed or tuber, or to the soil or water in which it is growing a fungicidally effective amount of a compound having the structural formula ##STR10## wherein X and Y are each independently hydrogen, halogen, or C₁ -C₆ alkyl;m and n are each independently an integer of 0, 1, 2 or 3; A is O or S; R, R₁ , R₂ and R₃ are each independently hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, nitro, NR₆ R₇ or SO₃ R₈, and when taken together, R and R₁ or R₁ and R₂ may form a ring in which RR₁ or R₁ R₂ is represented by the structure: --CH═CH--CH═CH--; R₄ is hydrogen, halogen, C₁ -C₈ alkoxy or C₁ -C₈ alkyl; R₅ is hydrogen, halogen, C₁ -C₈ alkoxy, C₁ -C₈ alkyl, NR₆ R₇, SO₃ R₈, hydroxy, oxo or phenyl optionally substituted with one or more halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups, provided that when R₅ is oxo, R₄ is not present; W is (CH₂)_(p) ; p is an integer of 0 or 1; and R₆, R₇ and R₈ are each independently hydrogen or C₁ -C₄ alkyl.
 6. The method according to claim 5 whereinX and Y are each independently hydrogen or halogen; m and n are each independently an integer of 0, 1 or 2; A is O; R, R₁, R₂ and R₃ are each independently hydrogen, C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, and when taken together R and R₁ may form a ring in which RR₁ is represented by the structure: --CH═CH--CH═CH--; R₄ is hydrogen; and R₅ is hydrogen.
 7. The method according to claim 6 wherein the compound is selected from the group consisting of1,1-diphenyl-2-oxa-7a-azonia-1-borataindan; 2,3-dihydro-1,1-diphenyl-2-oxa-9b-azonia-1-borata-1H-benzindene; 1,1-bis(p-chlorophenyl)-6-methyl-2-oxa-7a-azonia-1-borataindan; and 1,1-bis(p-chlorophenyl)-2-oxa-7a-azonia-1-borataindan. 